CN111747739A - Antiferroelectric ceramic material and preparation method thereof - Google Patents

Antiferroelectric ceramic material and preparation method thereof Download PDF

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CN111747739A
CN111747739A CN201910242446.8A CN201910242446A CN111747739A CN 111747739 A CN111747739 A CN 111747739A CN 201910242446 A CN201910242446 A CN 201910242446A CN 111747739 A CN111747739 A CN 111747739A
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王根水
韩刘洋
郭少波
董显林
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to an antiferroelectric ceramic material and a preparation method thereof, wherein the antiferroelectric ceramic material comprises the following chemical components: (Pb)xCaySrz)TiO3Wherein x is more than or equal to 0.3 and less than or equal to 0.45, y is more than or equal to 0.25 and less than or equal to 0.4, z is more than or equal to 0.2 and less than or equal to 0.45, and x + y + z =1, and the tolerance factor of the antiferroelectric ceramic material
Figure 366676DEST_PATH_IMAGE002
≤0.9985。

Description

Antiferroelectric ceramic material and preparation method thereof
Technical Field
The invention relates to an antiferroelectric ceramic material and a preparation method thereof, in particular to PbTiO3-CaTiO3-SrTiO3A ternary antiferroelectric ceramic material and a preparation method thereof belong to the technical field of ferroelectric ceramic materials.
Background
The antiferroelectric material has huge application prospect in the field of energy storage due to the special electrogenerated phase transition characteristic, and is developed rapidly. Because the ceramic has the advantages of simple preparation, lower cost, stable performance and the like, the pulse power device taking the antiferroelectric ceramic as a main energy storage element is widely developed and applied in the fields of national defense science and technology and civil use. Currently, research on antiferroelectric materials has focused on lead zirconate (PbZrO)3) Silver niobate (AgNbO)3) Sodium niobate (NaNbO)3) Doped solid solution of a base, wherein lead zirconate (PbZrO)3) And doped solid solutions thereof.
Strontium calcium titanate (CaTiO)3-SrTiO3CST) was reported in the last 90 th century. Ranjan et al (Journal of Physics: Condensed Matter 1999,11(10): 2233; Journal of Physics: Condensed Matter 1999,11(10): 2247; Physical review letters 2000,84(16),3726) reveal antiferroelectricity from a structural point of view by X-ray diffraction and neutron diffraction and, in combination with dielectric properties, give antiferroelectric phase regions in CST material systems. Subsequently, Lalla et al (Journal of Physics: Condensed Matter 2007,19(43): 436210; Solid State Sciences 2008,10(3):307- > 315; Journal of Physics: Condensed Matter 2008,20(32):325231) also structurally characterized the presence of the antiferroelectric phase in the CST by means of selective electron diffraction, among others. However, the antiferroelectric property of CST has been still in structural exploration without being proved in terms of macroscopic properties (such as double hysteresis loop). The only current report on the CST hysteresis loop is Mitsui et al (physical review 1961,124(5):1354) at 4.3K and Ca at 19960.04Sr0.96TiO3Middle measurement of hysteresis loop: at an extremely low electric field of 1.7kV/cm, Ca0.04Sr0.96TiO3Has a polarization intensity of 1.68. mu.C/cm2. While Ranjan et al (Physical review devices 2000,84(16),3726) did not observe a hysteresis loop when applied with an electric field of 60kV/cm in compositions with Ca contents above 0.12. The method for reducing the turning electric field by referring to the pure lead zirconate can compound the CST and the strong ferroelectric material together to ensure that the antiferroelectric-iron of the materialThe electric phase change turning electric field is lower than the breakdown electric field of the material, so that a double electric hysteresis loop of the material is observed.
Disclosure of Invention
In the present disclosure, the inventors are based on perovskite compounds (ABO)3) The stability of (c) can be judged by tolerance factor (t), and its expression is:
Figure BDA0002010075950000011
(1) (ii) a Wherein R isADenotes the radius of the A-site ion, RBDenotes the radius of the B site ion, ROThe oxygen ion radius (the ion radius for calculation of its tolerance factor is reported in Shannon (Acta Crystallographics 1976,32, 751)). It is further found that the t value when the perovskite structure can exist stably ranges from 0.88 to 1.09. The reduction of t is beneficial to the stability of the antiferroelectric phase; the increase of t is beneficial to the stability of the ferroelectric phase; the closer t is to the critical of the antiferroelectric phase and the ferroelectric phase, the smaller the turning electric field.
Therefore, the invention provides a brand-new antiferroelectric ceramic material, which comprises the following chemical components: (Pb)xCaySrz)TiO3Wherein x is more than or equal to 0.3 and less than or equal to 0.45, y is more than or equal to 0.25 and less than or equal to 0.4, z is more than or equal to 0.2 and less than or equal to 0.45, and x + y + z is 1, and the tolerance factor of the antiferroelectric ceramic material
Figure BDA0002010075950000021
In the present disclosure, the first pass is to mix PbTiO3Solid solution in CaTiO3-SrTiO3(CST) material, and can successfully measure the double hysteresis loop. The brand new antiferroelectric ceramic material provided by the invention breaks through the rigid course that the dual ferroelectric hysteresis loop cannot be measured by the CST antiferroelectric material for many years, and provides possibility for the later research of the application development of the CST-based antiferroelectric material. As shown in fig. 4 (which the inventors first plotted), the phase composition of the ceramic is affected by the tolerance factor of the ceramic composition. The disclosure is made by adding a specific content of PbTiO3With CaTiO3-SrTiO3Forming ternary system solid solution, and adjusting PbTiO3、CaTiO3、SrTiO3The content of the matrix components ensures that when the tolerance factor t of the ceramic is less than or equal to 0.9985, the obtained antiferroelectric ceramic material has an antiferroelectric double-hysteresis loop of a beam waist.
In another aspect, the present invention provides a method for preparing the antiferroelectric ceramic material, including:
selecting Pb3O4Powder, TiO2Powder, CaCO3Powder and SrCO3The powder is used as a raw material, weighed and mixed according to the composition chemical formula proportion of the antiferroelectric ceramic material, and then presintered at 850-900 ℃ to obtain ceramic powder;
pressing and molding the obtained ceramic powder, and then removing plastics to obtain a ceramic blank;
and sintering the obtained ceramic blank at 1260-1320 ℃ to obtain the antiferroelectric ceramic material.
Preferably, the mixing mode is wet ball milling mixing, and the raw materials are as follows: grinding balls: deionized water 1: (1.5-2.0): (0.7-1.0) for 24-48 hours.
Preferably, the ceramic powder and the binder are mixed, granulated, aged and sieved prior to press forming.
Moreover, preferably, the binder is polyvinyl acetate, and the addition amount of the binder is 6-8 wt% of the weight of the ceramic powder; the aging time is 22-26 hours.
Preferably, the pre-sintering treatment time is 1 to 3 hours.
Preferably, the temperature of the plastic discharging is 750-800 ℃, and the time is 1-3 hours.
Preferably, the time of the sintering treatment is 2 to 4 hours.
Preferably, the temperature rise rate of the sintering treatment is not higher than 2 ℃/min; the temperature rising rate of the pre-sintering treatment is not higher than 2 ℃/min.
On the other hand, the invention also provides an antiferroelectric ceramic element, which is characterized in that the antiferroelectric ceramic material is processed into required size, and the ferroelectric ceramic element is obtained after screen printing silver, drying and silver firing; the silver firing condition is that the temperature is kept at 650-750 ℃ for 20-40 minutes.
Has the advantages that:
a specific content of PbTiO with strong ferroelectricity3Introduction of CaTiO3-SrTiO3Formation of PbTiO in antiferroelectric materials3-CaTiO3-SrTiO3Ternary solid solution (PCST100x/100y/100z), and prepares PbTiO through the regulation and control of other components and tolerance factor (t is less than or equal to 0.9985)3-CaTiO3-SrTiO3The ternary antiferroelectric ceramic material is successfully used for measuring a double hysteresis loop at the temperature near room temperature. The invention breaks through the rigid that the dual ferroelectric hysteresis loop can not be measured by the CST antiferroelectric material for years by doping the new component, and provides possibility for researching the application development of the CST-based antiferroelectric material in the future.
Drawings
FIG. 1 shows (Pb)0.3Ca0.4Sr0.3)TiO3The hysteresis loop and the current-electric field curve of (Pb) can be seen from the figure0.3Ca0.4Sr0.3)TiO3The ceramic is in a beam waist double-electric hysteresis loop, has four obvious current peaks and is an anti-ferroelectric phase;
FIG. 2 shows (Pb)0.4Ca0.35Sr0.25)TiO3The hysteresis loop and the current-electric field curve of (Pb) can be seen from the figure0.4Ca0.35Sr0.25)TiO3The ceramic is in a beam waist double-electric hysteresis loop, has four obvious current peaks and is an anti-ferroelectric phase;
FIG. 3 shows (Pb)0.4Ca0.3Sr0.3)TiO3The hysteresis loop and the current-electric field curve of (Pb) can be seen from the figure0.4Ca0.3Sr0.3)TiO3The ceramic is in a beam waist double-electric hysteresis loop, has four obvious current peaks and is an anti-ferroelectric phase;
FIG. 4 shows (Pb)xCaySrz)TiO3The ternary phase diagram shows that in the composition range of x being more than or equal to 0.3 and less than or equal to 0.45, y being more than or equal to 0.25 and less than or equal to 0.4 and z being more than or equal to 0.2 and less than or equal to 0.45, when the tolerance factor t of the ceramic material is less than or equal to 0.9985, the antiferroelectric double-ferroelectric hysteresis loop can be measured, such asThe position indicated by the blue dots.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the chemical composition of the antiferroelectric ceramic material is: (Pb)xCaySrz)TiO3(PCST100x/100y/100z), wherein x is 0.3 ≦ 0.45, y is 0.25 ≦ 0.4, z is 0.2 ≦ 0.45, and x + y + z is 1. The invention is prepared by adding strong ferroelectric PbTiO3Introduction of CaTiO materials3-SrTiO3An antiferroelectric material. Using Shannon ionic radius
Figure BDA0002010075950000031
And calculating a tolerance factor, and enabling the antiferroelectric ceramic material to have an antiferroelectric double-ferroelectric hysteresis loop when the tolerance factor t of the ceramic is less than or equal to 0.9985.
The preparation method of the antiferroelectric ceramic material provided by the present invention is exemplarily described below.
With Pb3O4、TiO2、CaCO3And SrCO3The powder is used as a raw material, and the raw material is weighed and mixed according to the composition chemical formula of the ceramic to obtain mixed powder. Wherein, the mixing mode can be a wet ball milling method, and the raw materials are as follows: grinding balls: mixing deionized water (1.5-2.0) and deionized water (0.7-1.0) in a mass ratio of 24-48 hours, and drying.
Pressing the mixed powder into a raw material block, presintering at 850-900 ℃ for 1-3 hours, and finely grinding by a wet ball grinding method to obtain ceramic powder. Wherein the temperature rise rate of the pre-sintering treatment is not higher than 2 ℃/min. Wherein, the wet ball milling method comprises: according to the raw materials: grinding balls: mixing deionized water (1.5-2.0) and deionized water (0.7-1.0) in a mass ratio of 24-48 hours, and drying.
And adding the ceramic powder into a binder for granulation, aging, performing compression molding, and performing plastic removal to obtain a ceramic blank. Wherein the plastic removing system comprises: the temperature is 750-800 ℃, and the time is 1-3 hours. The binder may be polyvinyl acetate. The addition amount of the binder can be 6-8 wt% of the weight of the ceramic powder. For example, after the ceramic powder and the binder are uniformly mixed, the mixture is aged for 22-26 hours, and then is sieved to be used for preparing a ceramic blank.
And (3) putting the ceramic blank into a high-temperature furnace, covering the ceramic blank with ceramic powder with the same composition, heating to 1260-1320 ℃, preserving the heat for 2-4 hours, sintering under a closed condition, and cooling along with the furnace to obtain the antiferroelectric ceramic material. Wherein the temperature rise rate of the sintering treatment is not higher than 2 ℃/min.
The invention also provides an antiferroelectric ceramic element which is made of the antiferroelectric ceramic material. And processing the sintered ceramic material into a required size, screen-printing silver, drying and sintering the silver to obtain the ferroelectric ceramic element. The silver firing condition is that the temperature is kept at 650-750 ℃ for 20-40 minutes. The antiferroelectric ceramic element adopts a hysteresis loop measuring instrument TF Analyzer2000 of German AixACCT company to test a hysteresis loop, the obtained hysteresis loop is a double-electric hysteresis loop, and a current-electric field curve of the double-electric hysteresis loop has four current peak values.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
the antiferroelectric ceramic material comprises the following components: (Pb)0.3Ca0.4Sr0.3)TiO3
(1) Calculating each component Pb in the powder raw material according to the chemical formula3O4Powder and SrCO3Powder, CaCO3Powder and TiO2The powder is prepared according to the weight ratio and is mixed by a wet ball milling method according to the raw materials of ball and water with the ratio of 1:1.7:0.8The components are mixed evenly for 24 hours according to the mass ratio. Drying, sieving with 30 mesh sieve, briquetting in air atmosphere, heating to 900 deg.C at a temperature rise rate of 2 deg.C/min, and maintaining for 2 hr to synthesize the composition (Pb)0.3Ca0.4Sr0.3)TiO3The ceramic powder of (4);
(2) smashing the ceramic powder obtained in the step (1), sieving the smashed ceramic powder with a 30-mesh sieve, finely grinding the smashed ceramic powder for 24 hours by using a wet ball milling method, drying the finely ground ceramic powder, adding 8 wt.% of PVA (polyvinyl acetate) binder based on the weight of the powder, granulating, aging for 24 hours, sieving with a 20-mesh sieve, pressing the obtained powder into round pieces with the diameter of 15mm and the thickness of 2.5mm, and heating the round pieces to perform plastic discharge at 800 ℃ to obtain ceramic blanks;
(3) in order to prevent the lead component from volatilizing in the sintering process, the ceramic blank is put into an alumina crucible, the blank is covered by ceramic powder with the same composition, a ground cover is covered, the temperature is raised to 1280 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling;
(4) processing the sintered ceramic material sample into a sheet with the thickness of 0.5mm, cleaning, drying, screen-printing silver paste, drying again, heating to 700 ℃ at the temperature rise speed of 2 ℃/min, and carrying out heat preservation for 0.5 hour to burn the silver to obtain a ceramic element;
(5) the ceramic element prepared in this example 1 was measured for the hysteresis loop at room temperature using a hysteresis loop measuring instrument TFAnalyzer2000 of aixctt of germany, and the measurement frequency was 1Hz, and the results are shown in fig. 1 and table 1.
Example 2:
the material composition is as follows: (Pb)0.4Ca0.35Sr0.25)TiO3
The procedure of example 1 was repeated according to the above formulation. The measurement of the hysteresis loop at room temperature was performed on the ceramic element prepared in this example 2, and the results are shown in fig. 2 and table 1.
Example 3:
the material composition is as follows: (Pb)0.4Ca0.3Sr0.3)TiO3
The procedure of example 1 was repeated according to the above formulation. The measurement of the hysteresis loop at room temperature was performed on the ceramic element prepared in this example 3, and the results are shown in fig. 3 and table 1.
The main test results for each example are listed in table 1:
table 1 summarizes the chemical composition, tolerance factor and presence or absence of antiferroelectric phase of the antiferroelectric ceramic materials prepared in examples 1-3:
Figure BDA0002010075950000051

Claims (10)

1. an antiferroelectric ceramic material, characterized in that said antiferroelectric ceramic material has a chemical composition of: (Pb)xCaySrz)TiO3Wherein x is more than or equal to 0.3 and less than or equal to 0.45, y is more than or equal to 0.25 and less than or equal to 0.4, z is more than or equal to 0.2 and less than or equal to 0.45, and x + y + z =1, and the tolerance factor of the antiferroelectric ceramic material
Figure 916241DEST_PATH_IMAGE002
≤0.9985。
2. A method of preparing an antiferroelectric ceramic material according to claim 1, comprising:
selecting Pb3O4Powder, TiO2Powder, CaCO3Powder and SrCO3The powder is used as a raw material, weighed and mixed according to the composition chemical formula proportion of the antiferroelectric ceramic material, and then presintered at 850-900 ℃ to obtain ceramic powder;
pressing and molding the obtained ceramic powder, and then removing plastics to obtain a ceramic blank;
and sintering the obtained ceramic blank at 1260-1320 ℃ to obtain the antiferroelectric ceramic material.
3. The preparation method according to claim 2, wherein the mixing is performed by wet ball milling, and the raw materials are: grinding balls: deionized water 1: (1.5-2.0): (0.7-1.0) for 24-48 hours.
4. The production method according to claim 2 or 3, wherein the ceramic powder and the binder are mixed, granulated, aged and sieved before the press molding.
5. The preparation method according to claim 4, wherein the binder is polyvinyl acetate, and the addition amount of the binder is 6-8 wt% of the weight of the ceramic powder; the aging time is 22-26 hours.
6. The production method according to any one of claims 2 to 5, wherein the time of the pre-firing treatment is 1 to 3 hours.
7. The method according to any one of claims 2 to 6, wherein the temperature of the plastic discharge is 750 to 800 ℃ and the time is 1 to 3 hours.
8. The production method according to any one of claims 2 to 7, wherein the time of the sintering treatment is 2 to 4 hours.
9. The production method according to any one of claims 2 to 8, wherein a temperature rise rate of the sintering treatment is not higher than 2 ℃/min; the temperature rising rate of the pre-sintering treatment is not higher than 2 ℃/min.
10. An antiferroelectric ceramic component, characterized in that said antiferroelectric ceramic material of claim 1 is processed to a desired size, screen-printed with silver, baked and fired to obtain said ferroelectric ceramic component; and the silver firing condition is that the temperature is kept at 650-750 ℃ for 20-40 minutes.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6231779B1 (en) * 1997-10-20 2001-05-15 Massachusetts Institute Of Technology Piezoelectric actuators and method of making same
CN1524792A (en) * 2003-02-28 2004-09-01 新加坡纳米材料科技有限公司 Method for preparing crystalline state perovskite compounds powder
CN101050118A (en) * 2007-05-21 2007-10-10 北京化工大学 Method for preparing ceramics powder body of perovskite
CN106495688A (en) * 2016-09-27 2017-03-15 中国科学院上海硅酸盐研究所 One kind has field concurrently and causes to strengthen pyroelectric property and wide warm area electric card effect new ceramic material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6231779B1 (en) * 1997-10-20 2001-05-15 Massachusetts Institute Of Technology Piezoelectric actuators and method of making same
CN1524792A (en) * 2003-02-28 2004-09-01 新加坡纳米材料科技有限公司 Method for preparing crystalline state perovskite compounds powder
CN101050118A (en) * 2007-05-21 2007-10-10 北京化工大学 Method for preparing ceramics powder body of perovskite
CN106495688A (en) * 2016-09-27 2017-03-15 中国科学院上海硅酸盐研究所 One kind has field concurrently and causes to strengthen pyroelectric property and wide warm area electric card effect new ceramic material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘维良: "《先进陶瓷工艺学》", 31 August 2004, 武汉理工大学出版社 *

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